CN105175310B - Asymmetric aza diisoindole methylene compound and its synthesis and use of boron fluoride compound - Google Patents
Asymmetric aza diisoindole methylene compound and its synthesis and use of boron fluoride compound Download PDFInfo
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Abstract
The invention relates to synthesis and application of asymmetric aza-diisoindole methylene compounds and boron fluoride compounds thereof. The compound and the boron-fluorine compound thereof provided by the invention have the characteristics of high fluorescence quantum yield, large molar extinction coefficient, large Stokes displacement and the like. In addition, due to the unique asymmetric structure of an 'electron donor-pi conjugated system-electron acceptor' type, the compound provided by the invention can generate the phenomena of color fading and fluorescence quenching after dropping strong acid such as trifluoroacetic acid or trifluoromethanesulfonic acid into a solvent without containing N and O such as dichloromethane, and the organic solvent or compound containing N or O can restore the primary color and fluorescence after being added into the colorless solution, so that the compound can be used for detecting substances containing N atoms or O atoms. Meanwhile, the asymmetric aza-diisoindole methylene compound and the boron fluoride compound thereof provided by the invention also have important application values in the aspects of fluorescence sensing, cell imaging, photodynamic therapy and the like.
Description
Technical Field
The invention relates to a fluorescent dye, a preparation method and application thereof, in particular to a series of asymmetric aza-diisoindole methylene compounds, a preparation method of a boron-fluorine compound thereof and application of the compounds in detection of nitrogen-containing oxygen-containing compounds.
Background
Dipyrromethene fluoroboron compounds (BODIPY) are a novel fluorescent compound. The fluorescent quantum dot has high fluorescence quantum yield and molar extinction coefficient and good stability, so that the fluorescent quantum dot has good application in the fields of dyeing, fluorescence labeling, fluorescence analysis, photochemical sensing, immunolabeling, biological imaging, data storage, electroluminescence and the like. The absorption of the azadipyrromethene fluoroboron compound (Aza-BODIPY) is red-shifted compared to the dipyrromethene fluoroboron compound (BODIPY) without losing the excellent spectral properties of BODIPY. Thus, the method can be well applied to biological analysis and biological imaging.
There are three main methods for the synthesis of aza-BODIPY: 1)2, 4-diphenylpyrrole reacts with nitroso derivative thereof or pyrrole derivative reacts under the conditions of sodium nitrite, acetic acid and acetic anhydride to obtain aza-BODIPY intermediate, and then aza-BODIPY is obtained under the conditions of alkalinity and boron trifluoride ether; 2) the Michael addition product of cyanogen forms an aminopyrrole intermediate under the action of ammonia formate, and an aza-BODIPY intermediate is generated by heating; 3) the aza-diisoindole methylene compound is generated by the reaction of the benzo-dicyan and the Grignard reagent, and then coordinated with the boron fluoride to obtain the aza-BODIPY conjugated with aromatic ring. Only aza-BODIPY modified by 1, 3, 5 and/or 7-substituted can be obtained by the methods 1) and 2), and aza-BODIPY conjugated with aromatic ring can not be obtained. Compared with the 1, 3, 5 and/or 7 substituted and modified aza-BODIPY, the aza-BODIPY conjugated with aromatic ring has more novel optical properties and research prospect. [ see: (a) gorman, j.killoran, c.o 'shear, t.kenna, w.m.gallagher, d.f.o' shear, j.am.chem.soc.2004, 126, 10619; (b) s.o.mcdonnell, d.f.o' shear, org.lett.2006, 8, 3493; (c) gallagher, l.t.allen, c.o 'shear, t.kenna, m.hall, a.gorman, j.killoran, d.f.o' shear, br.j.cancer.2005, 92, 1702; (d) mcdonnell, m.j.hall, l.t.allen, a.byrne, w.m.gallagher, d.f.oshea, j.am.chem.soc.2005, 127, 16360; (e) hall, l.t.allen, d.f.o' Shea, org.biomol.chem.2006, 4, 776; (f) j.killoran, d.f.o' shear, chem.commun.2006, 1503; (f) muttagh, d.o.frimansson, d.f.o' Shea, org.lett.2009, 11, 5386; (g) palma, m.tasior, d.o.frimansson, t.truc Vu, r.meallet-Renault, d.f.o' Shea, org.lett.2009, 11, 3638; (h) g.satthyamorthi, m.l.soong, t.w.ross, j.h.boyer, heteroat.chem.1993, 4, 603; (i) e.b. knott, j.chem. soc.1947, 1196; (j) v.f.donyagina, s.shimizu, n.kobayashi, e.a.lukyanets, tetra.lett.2008, 49, 6152.)
However, the current methods are still relatively cumbersome on the one hand and have low yields. On the other hand, these methods cannot be used to synthesize aza-BODIPY of asymmetric structure. The method 1) can be used for synthesizing an asymmetric azadiisoindolylmethylene compound conjugated to an aromatic ring and a fluoroboron compound thereof, although an asymmetric dipyrromethene compound can be obtained by using some pyrrole derivatives.
Disclosure of Invention
The invention aims to provide a series of asymmetric aza-diisoindole methylene compounds and a boron fluoride compound thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
asymmetric aza diisoindole methylene compounds and their fluoroboron compounds having the following structure:
a substituent R ═ H or alkyl; the substituent Rx is one of the following: h, alkyl, aryl, alkoxy, aryloxy, alkylmercapto, arylmercapto.
A process for preparing the above-mentioned unsymmetrical azabicycloindolylmethylene compounds and their fluoroboron compounds which can be prepared by the reaction of:
the substituent R ═ alkyl; the substituent Rx is one of the following: h, alkyl, aryl, alkoxy, aryloxy, alkylmercapto, arylmercapto.
It comprises the following steps:
adding a solution of potassium tert-butoxide in N, N-dimethylformamide into a reaction vessel, and dissolving Rx-substituted phthalonitrile in the N, N-dimethylformamide, wherein Rx substituent is H, alkyl, aryl, alkoxy, aryloxy, alkyl mercapto or aryl mercapto. At normal temperature or lower temperature, dripping the Rx-substituted phthalic nitrile solution into a potassium tert-butoxide solution, detecting by a dot plate until the Rx-substituted phthalic nitrile is completely exhausted, continuing to stir for 60 minutes, dripping the obtained dark color solution into enough ice water, standing overnight, filtering, separating by a 100-mesh 140-mesh silica gel packed column, eluting methylene chloride and methanol, and evaporating the solvent to obtain a red solid which is an amino-substituted asymmetric aza-diisoindole methylene compound.
Adding an amino-substituted asymmetric aza-diisoindolylmethylene compound into a reaction container, adding a tetrahydrofuran solution dissolved with RNHR imine, wherein R is alkyl, carrying out reflux reaction until the raw material point disappears, carrying out spin drying, separating by using a 100-mesh and 140-mesh silica gel packed column, wherein an eluent is dichloromethane, evaporating the solvent, and recrystallizing by using dichloromethane/n-hexane to obtain a mauve solid which is a dialkyl amino-substituted asymmetric aza-diisoindolmethylene compound.
The resulting asymmetric azabicycloindolylmethylene compound described above was dissolved in methylene chloride and excess Triethylamine (TEA) and boron trifluoride-diethyl ether solution (BF) were added3·Et2O), stirring, refluxing, reacting, performing spot plate detection until the raw materials are completely consumed to obtain a bluish purple solution, quenching the reaction with water, washing the reaction mixture with distilled water, a saturated sodium bicarbonate aqueous solution and a saturated saline solution in sequence, drying, evaporating, concentrating, separating by using a 100-mesh 140-mesh silica gel packed column, wherein an eluent is dichloromethane, and evaporating the solvent to dryness to obtain a purplish red compound which is the asymmetric aza-diisoindole methylene fluoboron compound.
By using1H-NMR, UV-Vis, fluorescence spectrum, ESI-MS and crystal structure characterization and confirmation of the structures of the compounds (see the attached figure). Bruker DRX500 type nuclear magnetic resonance apparatus, the solvent is d-DMSO, CD2Cl2、CDCl3. Shimadzu UV-2700 type ultraviolet-visible spectrophotometer, CH2Cl2Is a solvent, and the scanning range is 250-800 nm; LCQ electrospray mass spectrometer (ESI-S, Thermo Finnigan);
a method for detecting and identifying molecules containing N atoms or O atoms by using the asymmetric aza-diisoindole methylene compounds and the fluoroboron compounds thereof. The steps are that; asymmetric aza-BODIPY is added into a solvent without N and O such as dichloromethane and the like, and strong acid such as trifluoroacetic acid or trifluoromethanesulfonic acid and the like is dropped into the solvent to generate fading and fluorescence quenching. Molecules containing N or O atoms are demonstrated if addition of organic solvents or compounds containing N or O to this colorless solution can restore the original color and fluorescence of the solution.
Compared with the prior art, the invention has the following remarkable advantages: 1. the first time, the N, N-dimethylformamide solution of potassium tert-butoxide is used as a base to react with the phthalic nitrile and the derivatives thereof. The azadiisoindole methylene compound and the boron fluoride compound thereof are synthesized from the phthalic nitrile and the derivatives thereof, the reaction condition is mild, the steps are simple, the yield is high, and the large-scale synthesis can be realized; 2) an aza-diisoindole methylene compound with an 'electron donor-pi conjugated system-electron acceptor' type asymmetric structure and a boron fluoride compound thereof are synthesized for the first time, and the compound has unique color change property; 3) the asymmetric aza-BODIPY compound provided by the invention can generate phenomena of color fading and fluorescence quenching after dropping trifluoroacetic acid or strong acid such as trifluoromethanesulfonic acid in a solvent such as dichloromethane and the like without containing N and O, and the colorless solution can recover the original color and recover the fluorescence after adding an organic solvent or compound containing N or O, so that the asymmetric aza-BODIPY compound can be used for detecting substances containing N atoms or O atoms.
Drawings
FIG. 1 is a nuclear magnetic spectrum of compound I-1.
FIG. 2 is a nuclear magnetic spectrum of compound I-2.
FIG. 3 is a nuclear magnetic spectrum of compound II-2.
FIG. 4 is the crystal structure of Compound II-2.
FIG. 5 shows compounds I-1, I-2 and II-2 in CH2Cl2Absorption spectra in solution.
FIG. 6 Spectrum and color change of Compound II-2 in dichloromethane drop-wise trifluoroacetic acid.
FIG. 7 shows the differences between compounds having similar structures in the dichloromethane solution (a) of compound II-2 and the dichloromethane solution of II-2 after the dropwise addition of trifluoroacetic acid.
Detailed Description
The organic fluorescent material provided by the invention uses phthalic nitrile and derivatives thereof in the synthesis process. By the following examples will
To facilitate a further understanding of the invention, without limiting the scope of the invention.
Example 1. Synthesis of Compound I-1:
potassium tert-butoxide (0.106g, 50mmol) was added to the reaction vessel, dissolved in 50ml of N, N-dimethylformamide, and then a solution of phthalodinitrile (6.4g, 50mmol) in 50ml of N, N-dimethylformamide was added dropwise to the above solution, stirred for 3 hours under ice bath, after which the dark solution obtained by the reaction was added dropwise to 500g of ice water and left to stand overnight. And filtering the solid, washing with water for three times, and drying to obtain a dark red solid which is a crude product of the compound I-1. Dissolving the crude product in dichloromethane, separating by using a 100-140-mesh silica gel packed column, wherein the eluent is dichloromethane and methanol, evaporating the solvent, and then recrystallizing by using dichloromethane/n-hexane to obtain the target compound I-1. I-1 was a dark red solid (4.4g, 69% yield); ms (esi): m/z 385.5[ M-H]-(ii) a Ultraviolet absorption 538nm (solvent is dichloromethane);1H NMR(500MHz，CDCl3) (ppm): 13.18(s), 8.22(1H, d), 8.07(1H, d), 7.91(1H, d), 7.82(1H, d), 7.69-7.74 (2H, m), 7.60(1H, d), 7.54(1H, t), 7.36-7.41 (2H, m), 7.21(1H, dd), 3.71(3H, s), 3.61(3H, s), and the nuclear magnetic map of which is shown in figure 1.
Example 2. Synthesis of Compound I-2:
compound I-1(3.90g, 10.1mmol) was charged into a reaction vessel, 100ml of a tetrahydrofuran solution of dimethylamine (2mol/L) was further added, and the mixture was heated to reflux, reacted for 12 hours, and then the solvent was dried by spinning. And dissolving the solid obtained by spin-drying in dichloromethane, separating by using a 100-mesh 140-mesh silica gel packed column, wherein an eluent is dichloromethane, evaporating the solvent, and then recrystallizing by using dichloromethane/n-hexane to obtain the target compound I-2. I-2 was a purple red solid (2.85g, 69% yield). Ms (esi): m/z 413.3[ M-H]-(ii) a Ultraviolet absorption 538nm (The solvent is dichloromethane);1H NMR(500MHz，CDCl3) (ppm): 13.18(s), 8.22(1H, d), 8.07(1H, d), 7.91(1H, d), 7.82(1H, d), 7.69-7.74 (2H, m), 7.60(1H, d), 7.54(1H, t), 7.36-7.41 (2H, m), 7.21(1H, dd), 3.71(3H, s), 3.61(3H, s), and the nuclear magnetic map thereof is shown in figure 2.
Example 3. Synthesis of Compound II-2:
compound I-2(2.07g, 5mmol) was charged into a reaction vessel, dissolved in 100ml of methylene chloride, 6ml of excess Triethylamine (TEA) was added thereto, and after stirring the mixture, a boron trifluoride-diethyl ether solution (BF) was added in three portions3·Et2O)9ml, stirring was continued for reflux reaction to give a bluish violet solution, plate detection was performed until the non-complexed product was consumed, and the reaction was then quenched with water. The reaction mixture was washed with distilled water, a saturated aqueous sodium bicarbonate solution and a saturated brine in this order, and the organic layer was dried over anhydrous sodium sulfate and concentrated by a rotary evaporator. Separating by using 100-140-mesh silica gel loaded column, wherein an eluent is dichloromethane, evaporating the solvent to dryness, and then recrystallizing by using dichloromethane/normal hexane to obtain the target compound II-2. II-2 was a purple red solid, (1.86g, 80% yield). Ms (esi): m/z 947.08[2M + Na ]]+；1H NMR(500MHz，CDCl3) (ppm): 8.27(1H, d), 7.90(1H, d), 7.84(2H, d), 7.72(1H, m), 7.70(1H, m), 7.62(1H, d), 7.55 to 7.58(2H, m), 7.48(1H, dd), 7.11(1H, dd), 3.78(6H, s); ultraviolet absorption is 591nm, and fluorescence emission is 654nm (the solvent is dichloromethane); the nuclear magnetic spectrum is shown in figure 3; the single crystal structure is shown in figure 4.
Example 4. Synthesis of Compound I-7:
in a single neck flask, 2.28g potassium tert-butoxide (20mmol) and 5ml anhydrous DMF were added, and nitrogen blanket was applied at 0 ℃. 1.84g of 4-tert-Butylphthalitrile (10mmol) was dissolved in 5ml of anhydrous DMF and added dropwise to the above solution, and the reaction system immediately turned bluish black. Monitoring the degree of reaction progress by using ultraviolet absorption spectrum, and specifically, using a liquid transfer gun to transfer 10 mu L of reaction liquid into 20 mu L of water to form a red turbid liquid, adding 5ml of dichloromethane into the turbid liquid, fully stirring to form a red solution, detecting the absorption spectrum of the dichloromethane solution at 500-600 nm, and adding 50g of ice water into the reaction liquid to quench the reaction when the intensity of the strongest absorption part begins to weaken along with the increase of time. Filtration and washing with water, collection of the solid, drying under vacuum, to give a dark red oily substance, which was directly dissolved in 20ml of dimethylamine in tetrahydrofuran (2mol/L) without further treatment, and reacted under reflux under nitrogen for 12 hours. After the reaction was completed, the solvent was spin-dried under vacuum, and the crude product was purified by column chromatography using silica gel as a packing material and methylene chloride as an eluent to give a red solid powder as compound I-7(585mg, yield: 30%). Ms (esi): m/z 581.5[ M-H]-.Anal.Calcd.for C38H42N6：C，78.32；H，7.26；N，14.42.Found：C，78.10；H，7.48；N，14.49.
Example 5 Synthesis of Compound I-12:
in a single neck flask, 2.28g potassium tert-butoxide (20mmol) and 5ml anhydrous DMF were added, and nitrogen blanket was applied at 0 ℃. 2.16g of 4-tert-butylmercaptophthalonitrile (10mmol) was dissolved in 5ml of anhydrous DMF, and was added dropwise to the above solution, and the reaction system immediately became bluish black. Monitoring the degree of reaction progress by using ultraviolet absorption spectrum, and specifically, using a liquid transfer gun to transfer 10 mu L of reaction liquid into 20 mu L of water to form a red turbid liquid, adding 5ml of dichloromethane into the turbid liquid, fully stirring to form a red solution, detecting the absorption spectrum of the dichloromethane solution at 500-600 nm, and adding 50g of ice water into the reaction liquid to quench the reaction when the intensity of the strongest absorption part begins to weaken along with the increase of time. FiltrationAnd washed with water, the solid was collected and dried under vacuum to give a dark red oily substance, which was directly dissolved in 20ml of a tetrahydrofuran solution of dimethylamine (2mol/L) without treatment, and reacted under reflux for 12 hours under nitrogen protection. After the reaction was completed, the solvent was spin-dried under vacuum, and the crude product was purified by column chromatography using silica gel as a packing material and dichloromethane as an eluent to give a red solid powder as compound I-12(746mg, yield: 33%). Yield: 33% MS (ESI): m/z 677.3[ M-H]-.Anal.Calcd.for C38H42N6S3：C，67.22；H，6.23；N，12.38.Found：C，67.42；H，6.12；N，12.26.
Example 6. Synthesis of Compounds I-17:
in a single neck flask, 2.28g potassium tert-butoxide (20mmol) and 5ml anhydrous DMF were added, and nitrogen blanket was applied at 0 ℃. 3.04g of 4, 4' -tert-butylphthalonitrile (10mmol) was dissolved in 5ml of anhydrous DMF, and was added dropwise to the above solution, and the reaction system immediately became bluish-black. Monitoring the degree of reaction progress by using ultraviolet absorption spectrum, and specifically, using a liquid transfer gun to transfer 10 mu L of reaction liquid into 20 mu L of water to form a red turbid liquid, adding 5ml of dichloromethane into the turbid liquid, fully stirring to form a red solution, detecting the absorption spectrum of the dichloromethane solution at 500-600 nm, and adding 50g of ice water into the reaction liquid to quench the reaction when the intensity of the strongest absorption part begins to weaken along with the increase of time. Filtration and washing with water, collection of the solid, drying under vacuum, to give a dark red oily substance, which was directly dissolved in 20ml of dimethylamine in tetrahydrofuran (2mol/L) without further treatment, and reacted under reflux under nitrogen for 12 hours. After the reaction was completed, the solvent was spin-dried under vacuum, and the crude product was purified by column chromatography using silica gel as a packing material and dichloromethane as an eluent to give a red solid powder as compound I-17(880mg, yield: 28%). Yield: 28 percent.1H NMR(500MHz，CD2Cl2)(ppm)：12.99(s)，8.41(1H，s)，8.04(1H，s)，7.97(1H，s)，7.94(1H，s)，7.90(1H，s)，3.68(3H，s)，3.49(3H，s)，1.58(9H，s)，1.49(9H，s)，1.44(9H，s)，1.39(9H，s)，1.38(9H，s)，0.96(9H，s).MS(ESI)：m/z 941.3[M-H]-.Anal.Calcd.for C50H66N6S6：C，63.65；H，7.05；N，8.91 Found：C，63.80；H，6.93；N，8.76.
Example 7. Synthesis of Compound II-7:
in a single-necked flask, 116mg of compound I-7(0.2mmol) was dissolved in 10ml of anhydrous dichloromethane, and 0.2g of triethylamine (2mmol) and 180. mu.L of boron trifluoride diethyl etherate (1.6mmol) were added, respectively, and the mixture was stirred under reflux for 5 hours under nitrogen. After the reaction was completed, the solvent was spin-dried under vacuum, and the crude product was purified by column chromatography using silica gel as a packing material and petroleum ether/ethyl acetate as an eluent to give a black solid powder as compound II-7(83.2mg, yield: 66%). Ms (esi): m/z 581.5[ M-H]-.Anal.Calcd.for C38H42N6：C，78.32；H，7.26；N，14.42.Found：C，78.10；H，7.48；N，14.49.
Example 8 Synthesis of Compound II-12:
in a single-neck flask, 136mg of compound I-12(0.2mmol) was dissolved in 10ml of anhydrous dichloromethane, and 0.2g of triethylamine (2mmol) and 180. mu.L of boron trifluoride diethyl etherate (1.6mmol) were added, respectively, and stirred under reflux for 5 hours under nitrogen. After the reaction was completed, the solvent was spin-dried under vacuum, and the crude product was purified by column chromatography using silica gel as a packing material and petroleum ether/ethyl acetate as an eluent to give a black solid powder as compound II-12(102mg, yield: 70%). Ms (esi): m/z 1475.3[2M + Na ]]+.Anal.Calcd.for C38H41N6BF2S3：C，62.80；H，5.69；N，11.56.Found：C，62.71；H，5.58；N，11.63.
Example 9 Synthesis of Compound II-17:
in a single-neck flask, 188mg of compound I-17(0.2mmol) were dissolved in 10ml of anhydrous dichloromethane, and 0.2g of triethylamine (2mmol) and 180. mu.L of boron trifluoride diethyl etherate (1.6mmol) were added, respectively, and stirred under reflux for 5 hours under nitrogen. After the reaction was completed, the solvent was spin-dried under vacuum, and the crude product was purified by column chromatography using silica gel as a packing material and petroleum ether/ethyl acetate as an eluent to give a black solid powder as compound II-17(142mg, yield: 72%).1H NMR(500MHz，CD2Cl2)(ppm)：8.47(1H，s)，8.15(1H，s)，8.07(1H，m)，7.95(1H，s)，7.93(1H，s)，3.76(6H，s)，1.67(9H，s)，1.50(9H，s)，1.44(9H，s)，1.40(9H，s)，1.32(97H，s)，1.04(9H，s).MS(ESI)：m/z 1013.3[M+Na]+.Anal.Calcd.for C50H65N6BF2S6：C，60.58；H，6.61；N，8.48.Found：C，60.73；H，6.74；N，8.30.
Example 10 detection of Compound II-2 and trifluoroacetic acid in dichloromethane of similar Compounds:
compound II-2(4.63mg) was dissolved in 100ml of methylene chloride to obtain a red solution having a concentration of 10-4mol/L, and a small amount of acetic acid and trifluoroacetic acid were added dropwise to the solution in two portions. The color of the solution dropwise added with acetic acid is not changed, while the dichloromethane solution dropwise added with trifluoroacetic acid gradually weakens the absorption at 500-600 nm and gradually strengthens the absorption at 300-400 nm, and the solution is colorless (see figure 6). The colorless solution is taken, a small amount of cyclohexane or dioxane, dodecanethiol or dodecanol, benzene or pyridine is added dropwise, and the color change is observed by naked eyes. It can be found that the addition of a small amount of a nitrogen-or oxygen-containing compound turns the colorless solution red. Therefore, two compounds with similar structures can be well distinguished by visual observation.
Claims (4)
1. A class of asymmetric aza-diisoindole methylene compounds and their fluoroboron compounds are characterized by their general formulas as shown in formula I and II:
wherein the substituent R is H or alkyl,
the substituent Rx is one of the following: h, alkyl, alkoxy, alkylmercapto.
2. The asymmetric aza-diisoindole methylene compounds and their fluoroboron compounds of claim 1, having the structural formula shown in formulas I-1 to I-20, II-1 to II-20:
3. a process for the preparation of unsymmetrical aza-diisoindole methylene compounds and their fluoroboron compounds as claimed in claim 1 or 2, characterized by the following reaction steps:
i) adding an N, N-dimethylformamide solution of potassium tert-butoxide into a reaction container, dissolving Rx-substituted phthalic nitrile in the N, N-dimethylformamide, wherein the Rx substituent is H, alkyl, alkoxy or alkylmercapto, dropwise adding the Rx-substituted phthalic nitrile solution into the potassium tert-butoxide solution at normal temperature or lower, detecting by a dot plate until the Rx-substituted phthalic nitrile is completely consumed, dropwise adding the obtained dark color solution into sufficient ice water, standing overnight, filtering, separating by using a 100-inch 140-mesh silica gel packed column, wherein the eluent is dichloromethane and methanol, and evaporating the solvent to obtain a red solid which is an amino-substituted asymmetric aza-diisoindole methylene compound;
ii) adding the amino-substituted asymmetric aza-diisoindole methylene compound into a reaction container, adding a tetrahydrofuran solution dissolved with RNHR imine, wherein R is alkyl, carrying out reflux reaction until the raw material point disappears, carrying out spin drying, separating by using a 100-mesh 140-mesh silica gel packed column, wherein an eluent is dichloromethane, evaporating the solvent to dryness, and recrystallizing by using dichloromethane/n-hexane to obtain a mauve solid which is the dialkyl amino-substituted asymmetric aza-diisoindole methylene compound;
iii) dissolving the obtained asymmetric aza-diisoindole methylene compound in dichloromethane, adding excessive triethylamine and boron trifluoride-diethyl ether solution, stirring and refluxing for reaction, performing dot-plate detection until the raw materials are completely consumed to obtain a blue-violet solution, then quenching the reaction with water, washing the reaction mixture with distilled water, a saturated sodium bicarbonate aqueous solution and saturated saline solution in sequence, drying, evaporating and concentrating, separating by using 100-one 140-mesh silica gel packed column, wherein the eluent is dichloromethane, and evaporating the solvent to dryness to obtain a purple compound which is the asymmetric aza-diisoindole methylene boron fluoride compound.
4. Use of an asymmetric aza-diisoindolylmethylene fluoroboron compound as claimed in claim 1 or 2 in fluorescence sensing.
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| CN103571458A (en) * | 2012-08-02 | 2014-02-12 | 中国科学院大连化学物理研究所 | Selenium-containing fluorine-boron dye fluorescent probe and application thereof in ClO<-> detection |
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